Method for producing ureaformaldehyde foams



June 1, 1965 D, s, sHRlvER ETAL METHOD FOR PRODUCING URBA-FORMALDEHYDE FOAMS Filed Dec. 4. 1961 ESA EN; S

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A :TIQRNE Y United States Patent 1186559 METHOD FR PRDUCEWG @REA- FFALDEHYDE FAMS Donald S. Shriver, Prince George County, Rob R. Macgregor, Hopewell, and William P. vMinore, Chester, Va., assigner-s to Allied Chemical Corporation, New York, NSY., a corporation of New Yori:

Filed Dec. 4, 1961, Ser. No. 155,83@ 2 Claims. (Cl. Zoli- 2.5)

This invention relates to an improved method for continuously producing urea-formaldehyde foams, and more particularly for continuously producing low density foams with closed cell structures. Such foams are particularly useful for insulation purposes.

Production of urea-formaldehyde foams has been carried out in the past, according to one procedure, by iujecting uncured resin into a stirred reaction vessel containing acidic liquid foam prepared by whipping air into water, foaming agent and acid, and curing the resin while it is distributed throughout the stirred foam.

Another procedure has 4been to dissolve gas or low boiling water-insoluble liquids under pressure into an uncured aqueous urea-formaldehyde resin and to cure the resin while releasing the pressure abruptly, thus producing foam.

The prior art processes have been primarily batch processes or semi-continuous processes which required turbulent mixing and which consequently resulted in non-uniform curing and frequent plugging of the apparatus with prematurely hardened product.

An object of the invention is to provide a process for continuously producing closed cell urea-formaldehyde foams in partially cured, liquid form which are suliiciently cured so as to be self-supporting, but ywhich remain sutilciently fluid to be blown directly into molds or other forming devices.

A further object of the invention is to provide a process for continuously producing a stream of partially cured urea-formaldehyde foam wherein mechanical agitation is avoided.

A still further object of the invention is to provide a process for blending an aqueous urea-formaldehyde resin solution with a foamed hardening solution wherein back blending is avoided.

These and other objects are accomplished by the apparatus illustrated and described herein and by the process of the invention, wherein an aqueous urea-formaldehyde solution is injected cocurrently into a stream of an aqueous acidic foam containing a surfactant and flowing at a space velocity between about 15,000 and about 25,000 hrl, maintaining the resulting resin-foam mixture under conditions of tubularllow at space velocities between about 1,500 and about 2,500 hrl, for a time suflicient to effect partial hardening of the foam to the extent that the foam is self-supporting but remains suiiiciently fluid to readily fill a molding cavity. Final curing may be accomplished at temperatures, for example, between about 20 C. and about 100 C. in a molding cavity.

In the drawing, the single figure illustrates, somewhat schematically, the apparatus of our invention. As illustrated, numeral 1 represents a vertical liquid-tight foam-v ing chamber, equipped at the bottom with an air inlet 2, controlled by valve 3, and leading to air distributor or sparger 4, the latter positioned within foaming chamber l. Leading into the foaming chamber is liquid inlet 5, conveniently terminating -above sparger d. Connected to foaming chamber is foam transfer line 6 6', which may optionally have attached thereto intermediate its extremities, a sump 7 and drain mechanism 8 for withdrawing any liquid that may be carried into the transfer tube 3,lbd,959. Patented. .lune l, 1965 from the foaming chamber. Transfer line 6 6 emp-ties through end chamber 9 into blending head itl which, as shown, terminates in a venturi-like restricted portion or reducing head il having a throat diameter between about one-third `and about one-half the diameter of blending head lli. Pipe 12. leads from a source of resin solution, not shown, through blending head 10, and terminates at the throat of venturi 1i. The venturi empties into cure tube 13 which has a diameter not greater than the diameter of the blending head, but may be greater than that of the venturi throat. The cure tube has a length of at least about 50, preferably between about 50 and about 250 times its diameter. The venturi or reducing head may be omitted provided the blending head has a diameter equal to or less than that of the cure tube. The cure tube may be of rigid or flexible construction, and is adapted for discharging its contents into containers, molds or spaces to be insulated, not shown, either without terminal ports, or through any desired shaped end member such as a spreader, fish tail or other desired member. The various members of the apparatus may have any suitable internal contiguration `or cross section and conveniently maybe substantially circular in cross-section. In any event, the internal walls of the apparatus should be substantially Ifree of bailles or obstructions which would tend to promote turbulence in the tlow of the foam or back mixing of foam and resin solution.

In operation, the liquid to be foamed is fed to foaming chamber 1 through liquid inlet 5 to Ithe desired liquid level. A controlled flow of air or other inert gas is then passed through gas inlet 2 and spargcr d int-o the reservoir of liquid to tbe foamed, regulated to produce the desired amount of foam. The flow of liquid to be foamed is then coordinated with the gas loW to maintain the desired liquid level in .foaming chamber l. and to produce the desired space velocity through the apparatus. An important feature in the maintenance of a controlled constant liquid level is that liquid is prevented from carrying over into .the transfer line with the forward moving foam. As both. liquid and gas are fed continuously into the chamber, foam emerges from the top of foaming chamber 1 and is propelled by the slight forward pressure from the gas inlet (ca. 5-20 lbs./ sq. in.) through transfer line 6 6', where :any excessliquid is trapped in sump 7, and proceeds to blending head 1li. Aqueous resin solution, preferably Ipartially cured, as described hereinafter, entering through inlet l2, empties into lthe foam at the point where the foam enters thereducing head or venturi l1, where it acts as an aspirator, and draws the foam into the resin stream causing thorough mixing and diffusion of foam and resin solutions without breaking the foam, as the mixture progresses into ythe curing tube 13. The blended resinous foam enters curing tube 13 with more than 99% of the air included in the minute cells of the foam. The length of the cure tube and the space velocity therethrough are regulated so as to provideV a curing time long enough so that lthe foam will not collapse upon emergence, but will remain sufficiently fluid to readily ll a molding cavity. l

In carrying out the process according to our invention, any conventional urea-formaldehyde solutions and conventional acidic foams may be used. We prefer, however, to utilize urea formaldehyde solutions in which the formaldehyde component and part of the urea are supplied in the form of a stabilized solution of ureaformaldehyde reaction products prepared according to the teachings of U.S.P. 2,652,377 issued September 15, 1953, and commerciallyl available under the trade name U.F. Concentrate-85. U.F. Concentrateis a clear, colorless, viscous, stabilized solution of formaldehyde and urea reaction products in a small amount of Water. It contains about 15% water and approximately viscousV and glass'like between `--20 and 30" C.A

85% solids, the latter combined in a formaldehyde to urea mol ratio of about 4.6 to 1, and the product typically contains about 59% formaldehyde and about 26% urea. lt ydoes not have a definite boiling point or freezing point. It starts to boil at about 100 C. and becomes extremely It is believed to be a mixtureV of polymethylol ureas insolution. The mixture is non-resinous and all the formaldehyde is available for resin-forming reactions.

Foam generation-In the process of our invention, foam is generated by continuously blowing air into the foaming chamber iilled with aqueous acidic foaming agent (hardener) solution. The air is passed through an aperture in the bottom of the foaming chamber, and

.the hardener solution is continuously fed into the lower portion of the foaming chamber. The air aperture may be a section of pipe drilled to give small openings, or it may be a porous metal or ceramic sparger which generates foam bubbles 0.1 to 0.6 mm. in diameter. The foam froths to the top'of the `foam generator at a velocity which should not exceed 2.5 ft./ sec. to minimize liquid hardener being carried forward with the foam. The line connecting the foam generator with the blending head may be iittedvwith a sump, if desired, to trap` liquid hardener passing with the foam from the foaming chamber, to prevent unfoamed hardener solution reaching the blending head which tends to cause plugging of the apparatus.

The hardener solution is an aqueous solution containing about 2% of a surfactant as foaming agent such as soap, alkyl aryl sulfonates or other conventional foaming agent and about 0.5% of a weakly ionized acid such as formic acid. The use of a weakly ionized acid (dissociation constant ca. 1.6X-4') is important to minimize Y prematurel hardening of the resin in the apparatus.

BlendingYfoam and resin.-When the foamedV hardener reaches the blending head, urea-formaldehyde resin solution is added to the foam. The weight ratio of hardener Blendv solution to resin solution is between 0.5 and 2.3. ing takes place as the foam and resin are movedptogether through the blending head at a space velocity in excess of 15,000 hr.1 (based on total volume of the blending.

The lower extremity of the blending tube conflow is suicient to retard mixing in the axial'direction.

Any signiticantYback mixing in the cure tube must be given reactor depends on various physical properties of given in thefollowing tabulation:

eddy streams or back-mixing. No mechanical agitation Y is used to accomplish` blending. This is important because mechanicalagitators would break the windows in a large portion of the'foam cells, producing an opencell foam. AgitatorsY would also cause considerable backmixing inrtheYblender which would contribute to a rapidV buildup of polymer on the moving parts of the apparatus, causing plugs and equipment shutdown.V

Resin-TheV urea-formaldehyde resin solution used in this process YshouldYhave a solids content of about -65%, a formaldehyde to urea mol ratio between and 2.0 andaviscosit'y of approximately 40-55 centipoise at 25 C. ,Theflinear velocity at the liquid resin sent Y to the blender'should'be at least 0.3 ftd/sec. to prevent plugging of the apparatus.

Suitable resin and hardener solutions for use inthe` process may be l"prepared asilatelyto al mold. v`Therefore, thispartially cured foam yis Vsent directly vto a curing tube where'suticient retention ltime is provded'for the cure tofreach the stage where 'f the foam will support itself. V'For accomplishing Vthis rei sult the iiow of the foam should be forward at a spaceA tube must be suchV that there is little or no back-mixing.

This type flow is tubularfow. Tubular ow occurs*Y the fluid, particularly the viscosity. VWe have found that tubular llow may be obtained with the urea-formaldehyde foam and a long trouble-free operating period obtained with linear velocities of 2 ft./sec. yor higher Yin a 1-inch diameter cure tube., In a Z-inch diameter cure tubeYequal results are obtained with linear velocities of 6 vft./sec. or more. Thus, two prime control requirements must be satisfied in the cure tube: tubular flow must be achieved and the curetime must be held in theV range where the product is cured farenough to support itself but not enough to set up or stick in the cure tube. Preferably, the diameterV of the curing tube is 40-200 times the diameter of the bubbles in the tube and the space velocity is about 1,500 h'r.1 to 2,500 hrrl. Y

The air or Vother inert gas sent tothe sparger should be at such a rate that essentially all the -air 99%) is occluded in foam bubbles. This is readily accomplished by adjusting the volume of air furnished to equal the volume of foam produced. On a volume basis, the ratio of air to liquids added in the process is preferably in the range of 5 to 55. Excess airshould be avoided. lf'excess air is employed, the windows are blownY out of the cell Walls as the foam passes through the cure tube in an incompletestate of cure. The cell walls are also broken if violent agitation or shear occurs. With theptubular ow curetube and a controlled velocity in the tube the foam emerges cured to the :extent that it willy support itself and may be suitably molded while the cure is completed. If desired, acid gases (such as VHC1 or SO2) or acid solution may be added to the foam as it emerges from the cure tube to facilitate the hardening of the foamg-ordinarily extra acid is not used. The cure tube may be constructed of either ilexible or rigid material, as desired.

A summary vof preferred conditions of operation is *Condition Range i Foam generation:

Foam former Air eductor,bubbler,sparger Y Foam transfer to blender Through a line fitted with a sump Y to remove unfoamed hardener. Foam blending:

Foam blender Y Venturi type, no moving parts. Ratio air/total liquids, vol./vol 5-55 Y Foam space velocity in 15,000-25,000.

blender, hr. 1 1. l Y v Type flow in blenden-; Tubular flow. Ratio hardener solution/resin 1-2. soln., wt./wt. I Y

- Foam eure: Y

Type apparatus, Cure tube. Type ilow'in eure-tube.; Tubular ilow. Portion of air occluded in 994-671,.' Y

foam bubbles. l I Y Space velocity of foam ln cure Lw-2,500.

Y tubehr.1. l Y Construction ot cure tube Rigid or iiexible.

V4ilfhe'effectiveness of the urea-formaldehyde foam gen- VV eratirng process and apparatus ofthe present invention areV further illustrated Vby the following example:l Y *f velocity of about V1500-2500 .hn-1. Flow in the curing fr Example V- A` {(A), 4Illzlir'dener solution wascontinuously 'fed throughY Y the hardener'inlet v5 to the foaming chamberl at a rate VComposition of 1800 grams (1760 crc.) perrminute with the following Component: Wt. Percent Water 97.55 Formic acid 0.50

Nacconal SZA (a commercially available foaming agent, a viscous liquid compound 80% alkyl aryl sulfonic acid and having a pH of 1.5 1.95

Air was simultaneously sent to the foaming chamber 1 through air inlet 5 at a rate of 2 ft.3/min. and injected by air sparger 4 to give foam containing bubbles primarily about 0.2-0.6 mm. in diameter. The foaming chamber consisted of a section of 11/2 in., Schedule 40 stainless steel pipe 13 in. long (lOl/2 in. above the hardener solution inlet). The foaming chamber contained an air sparger made of a porous stainless steel disk (Pall Corp.) 15/s in. in diameter with a mean opening size of 15 microns. The foam was frothed from the top of the foaming chamber at a space velocity of 3640 hr2-1 and sent through transfer line 6 through hardener sump 7 Where any liquid hardener solution was removed through drain 8 and discarded. This discarded hardener solution amounted to 8 percent of the total hardener charged. The foam, drained of liquid hardener passed through transfer line 6' to the blending head 10.

(B) Resin for use in the foaming apparatus was prepared and partially cured by the following procedure: To a 50-liter conical tank was added 18,000 grams water and 7,000 grams urea. The contents were agitated and heated to 90 C. and 20 kilograms of U.F. Concentrate- 85 (equivalent to 59% wt. HCHO-26% urea-15% water) was added slowly over a 2li-minute period. After the addition of UF-85, 10 ml. of conc. (89%) forrnic acid was added, bringing the solution pH to 5. The reaction temperature was maintained at 93 C. After 29 minutes, the viscosity had increased to 21 centipoise (taken at 41 C.). The resin formation reaction was stopped after 34 minutes by adding 14.1 ml. of 50% (wt.) aqueous sodium hydroxide solution and by cooling the contents quickly to 25 C. The viscosity was then 43.5 centipoise at 25 C. and resin pH was 7.1. To 45.37 pounds of the partially cured resin was added 1375 grams of urea and 367 grams ammonium bicarbonate. Viscosity of the nal resin was 45 centipoise at 25 C.

(C) The partially cured resin, described above, was continuously fed through resin inlet 12 at the rate of 900 gm. per minute (750 cc./min.) to the blending head 10; the hardener to resin weight ratio was 2. The blending head consisted of a 41/2 in. section of 11/2 in., Schedule 40 pipe (1.61 in. LD.) with a venturi on the lower extremity of the tube having a throat diameter of 0.74 in. The partially cured resin entered the blending head 1.1/2 in. from the lower end. The resin and oarned acid commingled as they passed through the blending head at a space velocity of 21,000 lnx-1, including the air and based on the total volume of the blending head. The air/total liquids volume ratio was 22.6, with 99-l% of the air contained in the small bubbles of the foam. Polymerization of the partially cured resin was reactivated when the hardener foam met the resin and further curing was begun.

(D) The curing foam emerged from the blending head 10 into the cure tube 13 at a rate of about 2 ft.3/min. and

passed through at a space velocity of 2200 hr. The cure tube was 1 in. LD. and 10 ft. long. The linear velocity in the cure tube was 6.11 ft./sec., well over the minimum required to give Tubular Flow in a 1 in. LD. tube. The foam left the cure tube in a continuous stream and was used to lill numerous large molds.

(E) The molded foam was dried and inspected with a stereoscopic microscope. The cell structure of the foam was completely closed with the cell walls (windows) intact. The cell size varied primarily between 0.33 and 0.58 mm. diameter. The density of the dried foam was 0.5 1b./ft.3.

While the above describes the preferred embodiments of our invention, it will be understood that departures may be made therefrom within the scope of the specification and claims.

We claim:

1. A process for continuously producing partially hardened closed cell structure urea-formaldehyde foams which comprises injecting a stream of aqueous urea-formaldehyde resin solution cocurrent into a stream of an aqueous acidic foam containing a surfactant and flowing under conditions of tubular flow at a space velocity between about 15,000 and about 25,000 hour-1; maintaining the resulting resinous foam mixture under conditions of tubular ow at space velocities between about 1,500 and about 2,500 hour-1 for a time sucient to eifect partial hardening of the foam to the extent that the foam is self-supporting but remains sufciently duid to readily till a molding cavity.

2. A process for continuously producing partially hardened, closed cell structure urea-formaldehyde resin foams, which comprises forming, from an aqueous acidic solution containing a surfactant as foaming agent, a stable foam having bubbles whose diameters are in the range between about 0.1 m. and about 0.6 mm., propelling said foam through a blending head at a space velocity between about 15,000 hour1 and about 25,000 hour-1, injecting cocurrent into said foam a stream of aqueous urea-formaldehyde resin solution in a weight ratio of foam to resin solution of between about 0.5 and about 2.3 in a zone of restricted flow whereby thorough blending of foam and resin takes place, propelling the thus blended resinous foam under conditions of tubular flow through a curing zone at a space velocity between about 1,500 hour-1 and about 2,500 hour-1 and a linear speed of at least about 0.3 feet per second for a period suicient to produce a self-supporting resinous foam.

References Cited bythe Examiner UNITED STATES PATENTS 2,813,780 11/57 Vieli 260-25 2,970,120 1/ 61 Kreidl et al. 260-25 3,006,871 10/ 61 Sunderland 260-2.5 3,026,183 3/62 Cole 23-252 3,035,902 5/ 62 Kurz 23-252 3,063,952 1l/62 Vieli 260-2.5

MURRAY TILLMAN, Primary Examiner.

LEON J. BERCOVITZ, Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,186,959 June l, 1965 Donald S. Shriver et al.

It s hereby certified that error appears in the above numbered patenfI reqlrng correction and that the said Letters Patent should read as correctedbelow.

Column 4, in the table, flrst Column, line ll thereof, for

-l 1 "hr.1 read hr. column 6, line 36, for "0.1 m read 0 l mm.

Signed and sealed this 2nd day of November l965,

(SEAL) Attest:

ERNEST W. SWIDER EDWARD J BRENNER Ailcsting Officer Commissioner of Patents 

1. A PROCESS FOR CONTINUOUSLY PRODUCING PARTIALLY HARDENED CLOSED CELL STRUCTURE UREA-FORMALDEHYDE FOAMS WHICH COMPRISES INJECTING A STEAM OF AQUEOUS UREA-FORMALDEHYDE RESIN SOLUTION CONCURRENT INTO A STREAM OF AN AQUEOUS ACIDIC FOAM CONTAINING A SURFACTANT AND FLOWING UNDER CONDITIONS OF TUBULAR FLOW AT A SPACE VELOCITY BETWEEN ABOUT 15,000 AND ABOUT 25,000 HOUR -1; MAINTAINING THE RESULTING RESINOUS FOAM MIXTURE UNDER CONDITIONS OF TUBULAR FLOW AT SPACE VELOCITIES BETWEEN ABOUT 1,500 AND ABOUT 2,500 HOUR -1 FOR A TIME SUFFICIENT TO EFFECT PARTICAL HARDENING OF THE FOAM TO THE EXTENT THAT THE FOAM IS SELF-SUPPORTING BUT REMAINS SUFFICIENTY FLUID TO READLIY FILL A MOLDING CAVITY. 